Detergent grade to C10 to C28 olefins, (C10 to C28 alkyl)benzenes and C10 to C28 alkyl) benzene sulfonates and process for preparing same using a phosphine containing catalyst

ABSTRACT

A dimerization process for producing linear and/or mono-branched C10 to C28 olefins using dimerization catalysts and new C10 to C28 olefins mixtures are disclosed. The C10 to C28 olefin product is especially useful for the production of biodegradable alkylbenzene sulfonates detergents and intermediates therefor.

This application is a continuation of application Ser. No. 515,798,filed Apr. 27, 1990 and now abandoned.

BACKGROUND OF THE INVENTION

This invention relates to a process and catalyst for the dimerization ofolefins to produce longer chained olefin products. In a further aspect,the invention relates to the production of olefins and alkylbenzeneswhich are especially useful as intermediates in the production ofalkylbenzene sulfonate detergents. The invention also relates to suchdetergents and their production.

One significant commercial application of longer chained olefins (e.g.,C₁₀ to C₂₈) is as intermediates in the production of alkyl aromaticsulfonate detergents. Since large amounts of such detergents areultimately released to the environment, the need for biodegradability iswell recognized. It is further well recognized that linear andmono-branched alkyl aromatic sulfonates are generally much more readilybiodegraded than multibranched alkyl aromatic sulfonates and, hence,much more desirable as detergents. Thus, the need exists for processeswhich efficiently produce high yields of C₁₀ to C₂₈ linear and/ormono-branched olefins or olefin mixtures which afford biodegradablealkylbenzene sulfonates.

U.S. Pat. No. 3,315,009, issued Apr. 18, 1967 to Engelbrecht et al.,discloses a two-dimerization step process for preparing C₈ to C₁₆olefins using a heterogeneous cobalt oxide catalyst. Patentee teachesthat it is preferred that the dimer feed to the second stagedimerization be substantially linear, but that the presence ofbranched-chain mono-olefins in the feed to the second stage up to 15% byweight is not deleterious.

U.S. Pat. No. 3,317,628, issued May 2, 1967 to Schuck et al., disclosesa two-dimerization step process for preparing higher olefins similar tothat described in the aforementioned U.S. Pat. No. 3,315,009, but usinga somewhat different heterogeneous cobalt catalyst. Patentee stressesone of the advantages of patentee's process is that the formation ofundesired isomers, such as 2-methylpent-2-ene is minimized if noteliminated. Patentee describes 2-methylpent-2-ene as an especiallyundesirable isomer in hexene fractions for the purpose of patentee'sprocess because it is not separated from n-hexene by commercial methodsof distillation and therefore requires special separation procedures orit must remain as an impurity.

U.S. Pat. No. 3,402,217, issued Sept. 17, 1968 to EngeIbrecht et al.,discloses a two zone polymerization process for preparing higher olefinsusing a molecular sieve or zeolite catalyst. Patentee teaches that aparticularly preferred mono-olefin dimer feed to the second zonepolymerization is one which contains no greater than 10% by weight ofbranched-chain mono-olefins and the remainder straight-chainmono-olefins. Patentee further teaches that generally ordinaryfractional distillation is adequate to purify the first dimerizationzone product, but that in addition to or in place of fractionaldistillation, other conventional separation or purification means suchas adsorbents, i.e., molecular sieves, solvent extraction, extractivedistillation, selective polymerization, isomerization, and the like maybe employed to conform the dimer product of the first-stage dimerizationto the feed requirements of the second-stage dimerization. Patenteestates that it is immaterial to patentee's invention what separationmeans is used for purifying the product of the first-stage dimerizationto meet the feed requirements of the second-stage dimerization, so longas such separation means provides the desired purification.

U.S. Pat. No. 3,409,703, issued Nov. 5, 1968 to Engelbrecht et al.,discloses a two-dimerization step process similar to that disclosed inU.S. Pat. No. 3,315,009, but using a modifying agent in the firstdimerization.

U.S. Pat. No. 3,424,815, issued Jan. 28, 1969 to Cannell et al.,describes the preparation of α-olefin oligomers using a catalystcomprising the product of certain nickel chelates with a halide-freeorgano-aluminum compound such as alkyl aluminum alkoxides. Patenteeteaches that the nickel chelating ligand-anion is substituted withelectron withdrawing groups, i.e., nitro, halo, cyano or carboalkoxy andthat superior results are obtained when the chelating ligands arehalogenated organic ligands.

U.S. Pat. No. 3,592,870, issued Jul. 13, 1971 to Dunn, discloses anolefin dimerization process using a catalyst formed from anorganoaluminum compound and one of the following nickel complexes: (a)bis(β-mercaptoethylamine)nickel (II) complex; (b)α-diketobis(β-mercaptoethylimine)nickel (II) complex; (c)S,S,-disubstituted bis(β-mercaptoethylamine)nickel (II) complex; or (d)S,S, -disubstituted-α-diketone bis(β-mercaptoethylimine)nickel (II)complex. Based on the product distribution shown in the examples of thispatent, the dimerization of propylene using patentee's catalystsresulted in C₆ olefin products containing 63 to 70% branched olefinsdepending on the particular catalyst used.

U.S. Pat. No. 3,910,869, issued Oct. 7, 1975 to Throckmorton, disclosesa process for the polymerization of butadiene and butadiene in mixturewith other diolefins to form polymers containing a high proportion ofbutadiene units in the cis-1,4 configuration. The process involvescontacting the monomer under solution polymerization conditions attemperatures ranging from -10° C. to 100° C. with a catalyst containingan organoaluminum compound, an organonickel compound and hydrogenfluoride.

U.S. Pat. No. 4,069,273, issued Jan. 17, 1978 to Komoto, describes aprocess for dimerizing low molecular weight linear α-olefins using acomplex of bis(1,5-cyclooctadiene)nickel and hexafluoro-2,4-pentanedioneas a homogeneous catalyst. Patentee describes his process as producing ahighly linear olefin product. U.S. Pat. No. 4,366,087, issued Dec. 28,1982 to Le Pennec et al., describes a process for oligomerizing olefinsusing a catalyst containing a hydrocarbyl aluminum halide and a nickelcompound having the formula (R₁ COO)(R₂ COO)Ni, wherein R₁ is ahydrocarbyl radical having at least 5 carbon atoms and R₂ is a haloalkylradical. As can be seen from the examples in this patent, patentee'sprocess afforded a product containing a large amount of branchedolefins. A number of catalyst systems used for the polymerization ofolefins are described in Chemical Review, 86 (1986), pp. 353-399.

U.S. Pat. No. 4,102,817, issued Jul. 25, 1978 to Throckmorton et al.,discloses a process for producing cis-1,4 polybutadiene by contactingbutadiene with a catalyst consisting of (1) at least one organoaluminumcompound, (2) at least one nickel compound, selected from nickel saltsof carboxylic acids, organic complex compounds of nickel and nickeltetracarbonyl, and (3) at least one hydrogen fluoride complex preparedby complexing hydrogen fluoride with a ketone, ester, ether, alcohol,nitrile or water.

U.S. Pat. No. 4,187,197, issued Feb. 5, 1980 to Kabanov et al.,discloses a method for dimerizing C₂ to C₄ olefins using a two componentcatalyst containing (1) a complex of a nickel salt with a tertiaryphosphine or tertiary phosphite and (2) an organoaluminum compound whichis a rubber selected from natural and synthetic carbo-chain rubber witha content of 2 to 50 mol % of Al Rx units wherein R is an alkyl with atmost 8 carbon atoms and x is a halogen, the atomic ratio of Al/Ni beingfrom 1:1 to 100:1.

U.S. Pat. No. 4,404,415, issued Sept. 13, 1983 to Gaillard, discloses aprocess for producing nonenes and dodecenes from propene. The repeatedaddition of propene to recycled hexene and nonene reaction products iscatalyzed by a catalyst substantially similar to that disclosed in U.S.Pat. No. 4,366,087.

U.S. Pat. No. 4,677,241, issued Jun. 30, 1987 to Threlkel, discloses aprocess for the oligomerization of a lower olefin having 2 to 8 carbonatoms by contacting the lower olefin with a catalyst containing atransition metal complex selected from complexes of nickel and palladiumwith a fluoro-organic thiol or sulfide ligand, having a single sulfuratom in a ligating position and wherein the carbon atoms adjacent thecarbon to which the sulfur atom is attached has at least one fluorosubstituent and with the proviso that the fluoro-organic thiol orsulfide does not contain any other ligating group or atom in a ligatingposition which will displace the fluoro as a ligand, and anorganometallic-reducing agent selected from borohydride andorganoaluminum halides and hydroxides.

Although the prior art speaks of highly linear products, seldom are suchresults obtained except at the cost of low yields or otherdisadvantages. For example, the two-step processes of the prior artwhich produce highly linear C₁₀ to C₁₅ olefin products also generallyrequire a highly linear intermediate product, thus effectively wastingsignificant yields of methyl pentenes which are obtained in the firststep reaction product. The prior art systems using heterogeneouscatalysts suffer from the usual contact problems incident to suchcatalysts. Moreover, the heterogeneous catalysts used by the prior artare frequently difficult and expensive to prepare. The use of halidemodifying agents also presents a problem since such agents are generallyvery corrosive and presents equipment problems.

One of the principal uses of C₁₀ to C₂₈ olefins is as intermediates fordetergents and lube oil additives, e.g., sulfonated alkyl benzenes. Whenused for detergents, the C₁₀ to C₂₈ olefin product should have a highproportion of linear or mono-branched olefins because detergentsproduced from predominantly linear olefins are generally more readilybiodegraded than those produced from highly branched olefins. Similarly,mono-branched olefins are generally more readily biodegraded thanmulti-branched olefins and, accordingly, more desirable for detergents.When used as an intermediate for lube oil additives, the C₁₀ to C₂₈olefin product should have a high proportion of mono-branched olefinsbecause lube oil additives produced from mainly mono-branched olefinshave premium properties such as low pour points or melting pointscompared to either linear or multi-branched olefins.

Thus, there exists a need for detergent grade C₁₀ to C₂₈ linear andmono-branched olefins and, accordingly, there exists a need for betterprocesses for preparing detergent grade C₁₀ to C₂₈ linear andmono-branched olefins.

SUMMARY OF THE INVENTION

In accordance with the present invention, there is provided a processfor preparing C₁₀ to C₂₈ linear and mono-branched olefins comprisingcontacting a C₅ to C₁₄ olefin feed with a dimerization catalyst which isselective to the production of linear and mono-branched olefins underdimerization conditions to produce a C₁₀ to C₂₈ olefin product whereinsaid dimerization catalyst is selected from the group consisting of:

(1) a mixture comprising:

(a) a nickel (II) compound having the formula NiXY wherein X is anorganic carboxy anion RCOO-- where R is an aliphatic hydrocarbyl groupof at least 4 carbon atoms and Y is a carboxylate or pentane dionylateanion;

(b) a phosphine compound having the formula PR'₃ where R' is an arylgroup; and

(c) an alkyl aluminum halide;

wherein components (1)(a), (1)(b) and (1)(c) are present in relativeamounts such that the P/Ni mole ratio is from about 0.75 to about 1.25and the Al/Ni mole ratio is from about 5.0 to about 15.0;

(2) a mixture comprising:

(a) a complex of a nickel (O) compound and a phosphine PR'₃ where R' isas defined above; and

(b) an alkyl aluminum halide or aluminum trihalide;

wherein components (2)(a) and (2)(b) are present in relative amountssuch that the Al/Ni mole ratio is from about 5.0 to about 7.0; and

(3) a mixture comprising:

(a) a mixture of a nickel (O) compound and a phosphine PR_(3') where R'is as defined above; and

(b) an aluminum trihalide;

wherein components (3)(a) and (3)(b) are present in relative amountssuch that the Al/Ni mole ratio is from about 5.0 to about 7.0 and theP/Ni mole ratio is from about 1.0 to about 2.0.

The present invention also provides the product produced by theabove-described process for making linear and mono-branched C₁₀ to C₂₈olefins.

Further provided in accordance with the present invention is a processfor preparing (C₁₀ to C₂₈ linear and mono-branched alkyl) benzenesulfonates comprising the steps of:

A. contacting a C₅ to C₁₄ olefin feed with a dimerization catalyst whichis selective to the production of linear and mono-branched olefins underdimerization conditions to produce a C₁₀ to C₂₈ olefin product whereinsaid dimerization catalyst is selected from the group consisting of:

(1) a mixture comprising:

(a) a nickel (II) compound having the formula NiXY

wherein X is an organic carboxy anion RCOO-- where R is an aliphatichydrocarbyl group of at least 4 carbon atoms and Y is a carboxylate orpentane dionylate anion;

(b) a phosphine compound having the formula PR'₃ where R' is an arylgroup; and

(c) an alkyl aluminum halide;

wherein components (1)(a), (1)(b) and (1)(c) are present in relativeamounts such that the P/Ni mole ratio is from about 0.75 to about 1.25and the Al/Ni mole ratio is from about 5.0 to about 15.0;

(2) a mixture comprising:

(a) a complex of a nickel (O) compound and a phosphine PR'₃ where R' isas defined above; and

(b) an alkylaluminum hallide or an aluminum trihalide;

wherein components (2)(a) and (2)(b) are present in relative amountssuch that the Al/Ni mole ratio is from about 5.0 to about 7.0; and

(3) a mixture comprising:

(a) a mixture of a nickel (O) compound and a phosphine PR'₃ where R' isas defined above; and

(b) an aluminum trihalide;

wherein components (3)(a) and (3)(b) are present ni relative amountssuch that the Al/Ni mole ratio is from about 5.0 to about 7.0 and theP/Ni mole ratio is from about 1.0 to about 2.0;

B. recovering linear and mono-branched C₁₀ to C₂₈ olefins from theproduct of step A;

C. contacting said linear and mono-branched C₁₀ to C₂₈ olefins withbenzene in the presence of an alkylation catalyst under reactiveconditions thereby producing a mixture of (C₁₀ to C₂₈ linear andmono-branched alkyl) benzenes; and

D. recovering said (C₁₀ to C₂₈ linear and mono-branched alkyl)benzenesand contacting said recovered (C₁₀ to C₂₈ linear and mono-branchedalkyl)benzenes with from about 1 to about 1.5 moles, based on sulfurcontent, of a sulfonating agent per mole of said (C₁₀ to C₂₈ linear andmono-branched alkyl)benzenes under reactive conditions thereby producinga mixture of (C₁₀ to C₂₈ linear and mono-branched alkyl)benzene sulfonicacids having the general formula ##STR1## wherein R¹ is linear ormono-branched C₁₀ to C₂₈ alkyl and neutralizing said (C₁₀ to C₂₈ linearand mono-branched alkyl)benzene sulfonic acids to yield a mixture of(C₁₀ to C₂₈ linear and mono-branched alkyl)benzene sulfonate salts.

The present invention also provides the (C₁₀ to C₂₈ linear andmono-branched alkyl)benzene sulfonate product produced by theabove-described process.

Also provided in accordance with another embodiment of the presentinvention is a process for preparing a mixture of (C₁₀ to C₂₈ linear andmono-branched alkyl)benzenes comprising the steps of:

A. contacting a C₅ to C₁₄ olefin feed with a dimerization catalyst whichis selective to the production of linear and mono-branched olefins underdimerization conditions to produce a C₁₀ to C₂₈ olefin product whereinsaid dimerization catalyst is selected from the group consisting of:

(1) a mixture comprising:

(a) a nickel (II) compound having the formula NiXY wherein X is anorganic carboxy anion RCOO-- where R is an aliphatic hydrocarbyl groupof at least 4 carbon atoms and Y is a carboxylate or pentane dionylateanion;

(b) a phosphine compound having the formula PR'₃ where R' is an arylgroup; and

(c) an alkyl aluminum halide;

wherein components (1)(a), (1)(b) and (1)(c) are present in relativeamounts such that the P/Ni mole ratio is from about 0.75 to about 1.25and the Al/Ni mole ratio is from about 5.0 to about 15.0;

(2) a mixture comprising:

(a) a complex of a nickel (O) compound and a phosphine PR'₃ where R' isas defined above; and

(b) an alkyl aluminum halide or aluminum trihalide;

wherein components (2)(a) and (2)(b) are present in relative amountssuch that the Al/Ni mole ratio is from about 5.0 to about 7.0; and

(3) a mixture comprising:

(a) a mixture of a nickel (O) compound and a phosphine PR₃ ' where R' isas defined above; and

(b) an aluminum trihalide;

wherein components (3)(a) and (3)(b) are present in relative amountssuch that the Al/Ni mole ratio is from about 5.0 to about 7.0 and theP/Ni mole ratio is from about 1.0 to about 2.0;

B. recovering linear and mono-branched C₁₀ to C₂₈ olefins from theproduct of step A; and

C. contacting said linear and mono-branched C₁₀ to C₂₈ olefins withbenzene in the presence of an alkylation catalyst under reactiveconditions thereby producing a mixture of (C₁₀ to C₂₈ linear andmono-branched alkyl)benzenes.

Another embodiment of the present invention provides the mixture of (C₁₀to C₂₈ linear and mono-branched alkyl)benzenes produced by theabove-described process.

DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS

The present invention provides a dimerization process and catalyst whichproduces excellent yields, typically 90% by weight or higher, of olefindimers in the C₁₀ to C₂₈ range, having a very high proportion of linearand mono-branched olefins, typically on the order of 75% by weight ormore. Thus, the present process is especially applicable for theproduction of olefins for use as intermediates used to preparedetergents or lube oil additives. Broadly, the dimerization process ofthe present invention comprises contacting a C₅ to C₁₄ olefin feed withthe present catalyst under reactive (dimerization) conditions. Theolefin feed should contain at least about 70% linear isomers which maybe either terminal or internal olefins. Linear α-olefins are notnecessary feedstocks for the present invention. Despite the dimerizationof completely internal olefins in the present invention, yields ofmono-branched and linear olefin dimers typically exceed 75%. This resultis surprising since doubly branched olefins are expected from internalolefin dimerization.

By way of illustration, when a C₆ olefin feed, such as a mixture ofhexenes, is dimerized, the resulting product would be expected tocontain a substantial amount of a multi-branched dimer. This isillustrated by the following general reaction scheme: ##STR2##

In contrast, when a mixture of hexenes is dimerized in accordance withthis invention, high proportions of linear and mono-branched C₁₂ olefinsare produced. A typical example of a linear C₁₂ olefin would be

    CH.sub.3 --CH.sub.2 --CH.sub.2 --CH.sub.2 --CH.sub.2 --CH . . . CH--CH.sub.2 --CH.sub.2 --CH.sub.2 --CH.sub.2 --CH.sub.3

(where the dotted line represents one possible position for the doublebond), and typical mono-branched C₁₂ olefins would be ##STR3## The firststep of the present process comprises contacting a C₅ to C₁₄ olefin feedwith a homogeneous dimerization catalyst under reactive conditions. Theolefin feed should contain at least about 70% linear olefins andalthough it may contain other alkenes it should be essentially free ofdienes.

Typically, the dimerization is conducted at temperatures in the range ofabout from about -10° C. to about 100° C., preferably from about 10° toabout 50° C. for about 1/2 to about 8 hours, preferably about 1 to about5 hours, using an olefin to catalyst mole ratio of about 200 to 20,000,preferably 1,000 to 10,000 moles of olefin per mole of catalyst. Thedimerization is generally conducted as a liquid phase reaction usingpressures in the range of about 0 to about 2 atmospheres, preferably 1to 2 atmospheres.

The selection of the catalyst for the dimerization is particularlyimportant. It has been found that the desired yields and selectivity canbe obtained by using certain nickel-containing catalysts as thedimerization catalyst, under the conditions indicated above. Thedimerization catalysts useful in this invention comprise homogeneousmixtures comprising:

(1) a mixture comprising:

(a) a nickel (II) compound having the formula NiXY wherein X is anorganic carboxy anion RCOO-- where R is an aliphatic hydrocarbyl groupof at least 4 carbon atoms and Y is a carboxylate or pentane dionylateanion;

(b) a phosphine compound having the formula PR'₃ where R' is an arylgroup; and

(c) an alkyl aluminum halide;

wherein components (1)(a), (1)(b) and (1)(c) ate present in relativeamounts such that the P/NI mole ratio is from about 0.75 to about 1.25and the Al/Ni mole ratio is from about 5.0 to about 15.0;

(2) a mixture comprising:

(a) a complex of a nickel (O) compound and a phosphine PR'₃ where R' isas defined above; and

(b) an alkyl aluminum halide or aluminum trihalide;

wherein components (2)(a) and (2)(b) are present in relative amountssuch that the Al/Ni mole ratio is from about 5.0 to about 7.0; or

(3) a mixture comprising:

(a) a mixture of a nickel (O) compound and a phosphine PR₃ ' where R' isas defined above; and

(b) an aluminum trihalide;

wherein components (3)(a) and (3)(b) are present in relative amountssuch that the Al/Ni mole ratio is from about 5.0 to about 7.0 and theP/Ni mole ratio is from about 1.0 to about 2.0.

Optionally, the catalyst may also contain a small amount of water whichhas the effect of increasing the rate of the catalytic dimerization.Generally, the amount of water employed will be an amount sufficient toincrease the rate of the catalytic dimerization. Typically, the amountof water used will be such that the water/Ni mole ratio in the catalystwill be from about 2:1 to about 5:1.

Examples of the nickel (II) compounds having the formula NiXY include,but are not limited to, bis-(2-ethylhexanoate)nickel; 2-ethylhexanoatenickel trihaloacetate; 2-ethylhexanoate nickel O-chlorobenzoate; and2-ethylhexanoate nickel acetylacetonate.

Examples of phosphines having the formula PR'₃ include, but are notlimited to, triphenyl phosphine, tritolyl phosphines; andtri(methoxyphenyl)phosphines.

Examples of alkylaluminum halides useful in the catalysts of the presentinvention include compounds having the formula R_(n) "AlZ_(3-n) where R"is a hydrocarbyl group, e.g., lower (C₁ to C₄) alkyl, Z is halide(preferably Cl) and n=1 or 2. Alkylaluminum dichlorides, such asethylaluminum dichloride, are examples of such compounds.

The nickel (O) compounds which are useful in the catalysts of thepresent invention are in general, nickel (O) compounds which are readilysoluble in an organic solvent. Examples of these nickel (O) compoundsinclude, but are not limited to, nickel carbonyl (i.e., Ni(CO)₄), andbis(triphenyl phosphine) nickel dicarbonyl.

The complexes of nickel (O) compounds and phosphine PR'₃ compoundsuseful in this invention typically have the general formula (CO)_(x)NiL_(4-x) where L is the phosphine ligand and x=1 or 2. Examples ofthese complexes include, but are not limited to,bis(triarylphosphine)nickel dicarbonyls, and triarylphosphine nickeltricarbonyls.

The aluminum trihalides useful in the practice of this inventioninclude, but are not limited to, AlCl₃. The dimerization catalysts ofthe present invention can be used in three forms. The first entails theuse of a mixture of a nickel (II) salt, NiXY, a phosphine PR'₃ (whichacts as a promoting ligand) and an alkylaluminum halide reducing agent.Preferably, X and Y are chosen to solubilize the complex in the olefinto be dimerized, although the NiXY salts need not be completely solublein the reaction medium, especially if the promoting phosphine complexeswith NiXY to aid solvation. Particularly suitable nickel salts are thebis-carboxylates such as bis-(2,ethylhexanoate) Ni (II) because thesesalts are relatively inexpensive and readily available. The phosphinepromoting ligand is of the general formula PR'₃ where R' is an aryl orsubstituted aryl group. Triphenyl phosphine is a particularly suitablepromoting ligand because it is readily available. The alkylaluminumhalide is of the general formula R"_(n) AlZ_(3-n), where R" is a lowmolecular weight alkyl, such as ethyl and n=1 or 2. Ethylaluminumdichloride is particularly suitable due to its availability and lowcost. The mole ratio of Ni:P:Al can vary and is chosen so that the P/Nimole ratio is from about 0.75 to about 1.25 and the Al/Ni mole ratio isfrom about 5.0 to about 15.0. Preferably, the P/Ni mole ratio is about1.0 and the Al/Ni mole ratio is from about 9.0 to about 13.0. A suitablecatalyst can also be prepared by exchanging AlCl₁₃ for some of theethylaluminum dichloride as long as the Al:Ni mole ratio remains above 9and the ethylaluminum dichloride:Ni mole ratio remains above 5.

The second form of catalyst entails the use of a mixture of a complex ofa nickel (O) compound and a phosphine PR'₃, and an aluminum trihalide.The complex can be prepared by the addition of the appropriate amount ofphosphine to, e.g., Ni (CO)₄ solutions in the olefin to be dimerized.The aluminum trihalide is most preferably the chloride or bromide ormixed salts of the two halogens. The mole ratio of Ni:P is mostpreferably 1:1 to 1:2. The mole ratio of Ni:Al is most preferably 1:5 to1:7.

The third form of catalyst useful in the present invention entails amixture which contains a mixture of a nickel (O) compound and aphosphine PR'₃ compound, and an aluminum trihalide.

The dimerization catalysts of this invention can be prepared bycontacting the appropriate components of the catalyst in the olefin tobe dimerized. Preferably, the components of the catalyst are not mixedtogether prior to their addition to the olefin feed, as this may causedecomposition of the catalyst. Typically, then, where the catalystemployed is a mixture of a nickel (II) compound, a phosphine PR' and analkyl aluminum halide, the nickel (II) compound and the phosphine may bepremixed and added to the olefin feed. The alkyl aluminum halide,however, should not be premixed with the nickel (II) compound andphosphine; rather, it should be added to the olefin feed (which alreadycontains the nickel (II) compound and phosphine compound) at the time itis desired to begin the reaction. Added solvents, such as chlorobenzenemay be used and do not detract from catalyst performance. Water may beadded up to the mole ratio of 5:1 water to nickel to increase the rateof catalytic olefin dimerization. The catalyst is typically prepared attemperatures in the range of from about -10° C. to about 100° C.,preferably from about 25° C. to about 50° C.

Where the dimerization is conducted as a batch process, the catalyst canbe conveniently prepared in situ in the reactor. The dimerization canalso be conducted as a continuous, semi-batch or multi-step process. Thedimerization can be conducted using suitable equipment and processdetail such as are conventionally employed in this art. Typically, thedimerization is conducted as a liquid phase reaction by contacting theolefin feedstock, which can be a single olefin or, as is frequently thecase, a mixture of olefins, with the present catalyst at temperatures inthe range of from about -10° C. to about 100° C., preferably from about25° C. to about 50° C., using a feedstock to catalyst mole ratio ofabout 1000 to 100,000. The dimerization is generally conducted atpressures below 2 atmospheres, and preferably sufficient to maintain aliquid phase system, e.g., at about 0 to about 2 atmospheres.

The present process and catalyst is especially useful for thedimerization of C₅ to C₇ olefins having a high degree of linearity toproduce high yields of C₁₀ to C₁₄ olefins containing a high proportionof linear and mono-branched isomers. Similarly, the present process isuseful for the dimerization of C₇ to C₁₄ olefins having a high degree oflinearity to produce high yields of C₁₄ to C₂₈ olefins containing a highproportion of mono-branched isomers. The product dimers can be isolatedfrom the reaction product mixture by any suitable procedure, forexample, distillation, extraction, and the like. Unreacted feedstock canbe recycled back to the initial feedstock.

The (C₁₀ to C₂₈ linear and mono-branched alkyl)benzenes of thisinvention can be prepared by contacting the aforedescribed C₁₀ to C₂₈olefin product with benzene in the presence of a suitable alkylationcatalyst (e.g., hydrogen fluoride, aluminum chloride, and the like)under reactive conditions.

Typically, where hydrogen fluoride is used as the catalyst, thealkylation is conducted at temperatures in the range of about from -20°to 65° C., preferably 0° to 55° C., for about 5 seconds to 4 hours,preferably 10 seconds to 2 hours, using mole ratios in the range ofabout from 5 to 50, preferably 10 to 20 moles of benzene per mole ofolefin and catalyst mole ratios in the range of about from 0.25 to 4,preferably 1 to 1.5 moles of benzene per mole of catalyst (i.e.,hydrogen fluoride). Because the presence of water in reactions usinghydrogen fluoride is known to present corrosion problem, the alkylationis preferably conducted under anhydrous conditions. The (C₁₀ to C₂₈linear and mono-branched alky)benzene(s) can be recovered from thereaction product by any suitable procedure, for example, by phaseseparating the (C₁₀ to C₂₈ linear and mono-branched alkyl)benzene-richproduct from the hydrogen fluoride phase; neutralizing any remaininghydrogen fluoride in the (C₁₀ to C₂₈ linear and mono-branchedalkyl)benzene phase; and removing unreacted benzene by distillation.

In the case where aluminum chloride is used as the catalyst, thereaction is conditioned in the presence of acid at temperatures in therange of about 0° to 75° C., preferably 25° to 50° C. for about from 1/2to 4 hours, preferably 1 to 2 hours using about from 5 to 50, preferably10 to 20 moles of benzene per mole of olefin and about from 2 to 8,preferably 3 to 5 moles of benzene per mole of aluminum chloridecatalyst. Typically, the presence of the acid is ensured by simplysaturating the benzene reactant with an acid such as hydrogen chloride.The (C₁₀ to C₂₈ linear and mono-branched alkyl)benzene product can berecovered from the reaction product by any suitable procedure such as,for example, aqueous extraction to remove aluminum chloride followed byneutralization and distillation. The (C₁₀ to C₂₈ linear andmono-branched alkyl)benzene product can be separated from the reactionproduct mixture by any suitable procedure. Typically, the catalyst issimply decanted off and any remaining catalyst reaction mixtureneutralized. The reaction product can then be purified by distillationto remove unreacted benzene, etc.

Regardless of the catalyst used, the alkylation is typically conductedas a liquid phase reaction and is typically conducted at pressures inthe range of about from 1 to 10 atmospheres, preferably 1 to 5atmospheres.

The (C₁₀ to C₂₈ linear and mono-branched alkyl)benzene sulfonates ofthis invention may be prepared by sulfonating the (C₁₀ to C₂₈ linear andmono-branched alkyl)benzenes described above. The sulfonation can beconducted by contacting the (C₁₀ to C₂₈ linear and mono-branchedalkyl)benzene product of the aforedescribed process with a sulfonatingagent, either neat, or optionally in an inert organic solvent or liquidmedium, under reaction conditions. The sulfonation can also be conductedin the presence of a moderating agent, such as, for example, dioxane.The modifying agent (e.g., dioxane) complexes with the sulfonatingagent, thus moderating the speed or intensity of the reaction.

The sulfonation is typically conducted at temperatures in the range ofabout from -40° to 100° C., preferably 0° to 50° C. for about from 1 to20 hours, preferably 1 to 10 hours using pressures of about from 1/2 to5 atmospheres, preferably 1 to 2 atmospheres. Typically, about from 1 to1.5, preferably about from 1.05 to 1.25 moles, based on sulfur, ofsulfonating agent are used per mole of (C₁₀ to C₂₈ linear andmono-branched alkyl)benzene. Under these conditions, onlymonosulfonation of the phenyl moiety of the alkylbenzene occurs.

Suitable sulfonating agents which can be used include, for example,sulfur trioxide, sulfuric acid, chlorosulfonic acid, and the like.Suitable inert organic solvents which can be used include, for example,methylene chloride, dichloroethane, trichloroethane, tetrachloroethane,and the like. Also, although an organic solvent could be used, it isgenerally preferable to conduct the sulfonation neat.

Since the product of the sulfonation is an acid, i.e , ##STR4## whereinR¹ is C₁₀ to C₂₈ linear and mono-branched alkyl it is necessary toneutralize the acid to permit its use as a detergent. The sulfonic acidproduct (I) can be neutralized by simple neutralization with a base toyield the corresponding sulfonate salt. The neutralization can beconveniently conducted in situ with the sulfonation reaction productmixture. [Any excess sulfonating agent can be simply neutralized in situalong with the sulfonic acid product (I).]

Typically, the neutralization is conducted at temperatures in the rangeof about from 0° to 60° C. and pressures of about from 1 to 2atmospheres using about from 1 to 1.1 mole equivalents of base per moleequivalent of sulfonate in the alkylbenzene. Suitable bases which can beused include, for example, alkali metal hydroxides, alkali earthhydroxides, ammonium hydroxides, quaternary ammonium hydroxides, amines,and the like. Typically, the base is added as an aqueous solution.Generally, the selection of the base will be a matter of economics, andfor this reason, sodium hydroxide is preferred because it gives goodresults and is relatively inexpensive. Suitable inert organic solventswhich can be used include the same solvents as listed above with respectto the sulfonation. However, typically a solvent is not used becausegenerally it is not necessary and merely adds another separation step toremove the solvent.

The (C₁₀ to C₂₈ linear and mono-branched alkyl)benzene sulfonate can berecovered from the reaction mixture by any suitable procedure or thereaction mixture can be simply concentrated by evaporating off wateradded with the base. Any small amounts of unreacted (C₁₀ to C₂₈ linearand mono-branched alkyl)benzene in the reaction product can be removedby a variety of procedures used in the detergent art, etc., includingextraction.

The (C₁₀ to C₂₈ linear and mono-branched alkyl)benzene sulfonates can beused as detergents in pure form or can be formulated with a variety ofbuilders (sequestering agents) and/or additives such as, for example,are conventionally used in the detergent art.

The present processes and process steps can be conducted as batch,semi-continuous or continuous operations or as a combination of suchoperations.

It should also be appreciated that where typical or preferred processconditions (e.g., temperatures, times, mole ratios, catalyst ratios,etc.) have been given, that other process conditions could also be used.Optimum reaction conditions (e.g., temperature, reaction time, reactantratios, catalyst ratios, solvents, etc.) may vary with the particularreactants, catalysts, or solvents used, but can be determined by routineoptimization procedures.

A further understanding of the invention can be had from the followingnonlimiting examples.

EXAMPLE 1

336 Grams of hexenes (containing 90% n-hexenes and 10% methyl-pentenes)was reacted with 0.69 g of nickel bis-(2-ethylhexanoate), 0.524 mg oftriphenyl phosphine, and 2.73 g of ethyl aluminum dichloride. After 3hours of reaction at between 35° C. and 55° C., 51% of the hexenes hadreacted. (The percentage of hexenes which react can be increased underdifferent reaction conditions.) The product of these reacted hexenes was92% dodecenes. 87% of those dodecenes were linear or mono-branchedstructures.

Analysis of the unreacted starting material showed that the hexenesreacted in preference to the methyl pentenes. The original startingmaterial contained 90% n-hexenes and 10% methyl pentenes, whereas thestarting material which remained unreacted after dimerization contained83% n-hexenes and 17% methyl pentenes. Thus, the relative amount ofmethyl pentenes had increased, which means that the n-hexenes reactedpreferentially.

Benzene alkylation using these dodecenes (see Example 5) using HFcatalyst yielded more than 97% dodecylbenzenes. Less than 1% of loweralkylbenzenes were produced by olefin fragmentation, even whenalkylation was carried out at 30° C.

EXAMPLE 2

504 Grams of hexenes (containing 75% n-hexenes and 25% methyl-pentenes)was reacted with 1.035 g of nickel bis(2-ethylhexanoate), 0.79 g oftriphenyl phosphine, and 3.92 g of ethyl aluminum dichloride. After 3hours of reaction at between 35° C. and 55° C., 47% of the hexenes wereconverted to products which contained 89% dodecenes. 81% of thosedodecenes had linear or mono-branched structures. As in Example 1, then-hexenes had reacted in preference to the methyl pentenes. Benzenealkylation with these dodecenes using HF catalyst yielded greater than97% dodecyl benzenes with less than 1% of lower alkylbenzenes formed byfragmentation.

EXAMPLE 3

Side-by-side experiments were carried out to demonstrate the beneficialeffect of water on the rate of catalytic olefin dimerization. In run A,16.8 g of hexenes (containing 90% n-hexenes and 10% methyl-pentenes) wasreacted with 34 mg of nickel bis(2-ethylhexanoate), 26 mg of triphenylphosphine and 127 mg of ethyl aluminum dichloride in 0.7 g ofchlorobenzene. A duplicate reaction (run B) was run with 27 mg of wateradded to the reaction mixture. After 2 hours of reaction at between 25°C. and 40° C., run A had been converted to 29% products while run B hadbeen converted to 37% products. The dodecenes from both runs were nearlyidentical, each containing 87% linear and mono-branched structures.Thus, the activity of the water promoted reaction is clearly superior tothat without water.

COMPARATIVE EXAMPLE A

15.1 Grams of hexenes (containing 75% n-hexenes and 25% methyl-pentenes)was reacted with 34 mg of nickel bis(2-ethylhexanoate), 28 mg oftricyclohexyl phosphine, and 127 mg of ethyl aluminum dichloride in 0.9g of chlorobenzene. After 3 hours of reaction at between 25° C. and 35°C., only 16% of the hexenes were converted to products. The dodecenesproduced contained only 61% linear and mono-branched structures. Thisexample demonstrates the poor results obtained when a trialkyl phosphineis used in the catalyst instead of a triaryl phosphine. When thetricyclohexyl phosphine was used, the result was low reaction rates, andpoor linear and mono-branched dodecene selectivity.

EXAMPLE 4

28 Grams of 1-octene was reacted with 34 mg of nickelbis(2-ethylhexanoate), 26 mg of triphenyl phosphine, and 127 mg of ethylaluminum dichloride. Analysis of the reaction mixture after 15 minutesof reaction showed that less than 5% 1-olefin remained although lessthan 20% of the octenes had been converted to dimers. After 4 hours ofreaction at between 35° C. and 45° C., 37% of the octenes were convertedto oligomers, 95% of which were hexadecenes. 90% of those hexadeceneshad linear and mono-branched structures.

EXAMPLE 5

This example demonstrates the utility of the above dodecenes asintermediates for biodegradable alkyl benzene sulfonates and theproduction of such sulfonates. 44 Grams of the dodecene product isolatedfrom Example 1 was mixed with 283 g of benzene. This mixture wascontinuously pumped into a reaction solution containing 100 g benzeneand 1492 ml of anhydrous hydrogen fluoride in a well-stirred stainlesssteel autoclave in which the reaction temperature was maintained at 30°C. The reaction mixture was stirred for 20 seconds, and then allowed tosettle for 80 seconds. Phase separation occurred after stirring wasstopped and the hydrocarbon layer was recovered and neutralized withcaustic and washed with water and dried over sodium sulfate. The acidlayer was reused for further alkylations with results substantiallyidentical to this reaction. GC analysis indicated that less than 2% ofthe dodecene had fragmented. The yield of dodecyl benzene was in excessof 95%. The remaining alkylate consisted of dialkylbenzenes. The excessbenzene was stripped off and the dodecyl benzene was purified bydistillation.

The dodecyl benzene product was sulfonated using standard SO₃ /airsulfonation reaction conditions. The alkylbenzene was sulfonated in awell-stirred water jacketed reactor equipped with a gas immersion inlettube. A 10% molar excess of SO₃ was added at a rate of about 1/2g/minute (for a 100-gram batch of alkylate) as a 6% mixture in dry airthrough the gas immersion inlet tube. Run temperature was maintainedbetween 35° C. and 50° C. by the 35° C. water jacket. After the SO₃ hadbeen added, the sulfonate mixture was cooled, and neutralized withaqueous sodium hydroxide until the pH was 7.5 to 8.0.

The biodegradability of this alkyl benzene sulfonate was determinedusing a hybrid modification of the standard ASTM test method ASTM D 2667designated biodegradability of alkylbenzene sulfonates, and the StandardOECD Screening Test for primary biodegradability of syntheticsurface-active agents. This test measures biodegradability by measuringloss of specific surface activity of the alkylbenzene sulfonate. Thus,the greater the loss of surfactant activity, the greater thebiodegradability. The results of this test are shown in Table I below interms of percent retention of surface activity. Hence, the lower thepercent retention, the greater the biodegradability. In addition, astandard (linear alkyl)benzene sulfonate known to be biodegradable and astandard (branched alkyl)benzene sulfonate known to be relativelynonbiodegradable were tested for comparison.

The samples were tested at a concentration of between 2 to 20 ppm in astandard nutrient solution. The solutions were inoculated with a 1 to10% solution of a sewage effluent to initiate biodegradation. Surfaceactivity was measured using the ASTM D 2330-82 procedure for methyleneblue active substances. The results are shown in Table I as a functionof time after inoculation.

                  TABLE I                                                         ______________________________________                                                            Percent Surface                                                               Activity Remaining                                                            Day 7  Day 10                                             ______________________________________                                        Standard (Linear Alkyl)benzene                                                                      5        3                                              Sulfonate                                                                     Standard (Branched Alkyl)benzene                                                                    88       56                                             Sulfonate                                                                     Dodecyl Benzene Sulfonate from                                                                      6        3                                              Example 5                                                                     ______________________________________                                    

As can be seen from the results recorded in Table I, the alkylbenzenesulfonate derived from the olefin of this invention biodegradessubstantially the same as the standard (linear alkyl)benzene sulfonate.This was further demonstrated by satisfactory biodegradation in thesemi-continuous activated sludge confirmatory test, in which thesulfonate of this invention and the standard (linear alkyl)benzenesulfonate were indistinguishable.

What is claimed is:
 1. A process for preparing C₁₀ to C₂₈ linear andmono-branched olefins comprising contacting a C₅ to C₁₄ olefin feed witha dimerization catalyst which is selective to the production of linearand mono-branched olefins, under dimerization conditions to produce aC₁₀ to C₂₈ olefin product wherein said dimerization catalyst is selectedfrom the group consisting of:(1) a mixture comprising:(a) a nickel (II)compound having the formula NiXY wherein X is an organic carboxy anionRCOO-- where R is an aliphatic hydrocarbyl group of at least 4 carbonatoms and Y is a carboxylate or pentane dionylate anion; (b) a phosphinecompound having the formula PR'₃ where R' is an aryl group; and (c) analkyl aluminum halide; wherein components (1)(a), (1)(b) and (1)(c) arepresent in relative amounts such that the P/Ni mole ratio is from about0.75 to about 1.25 and the Al/Ni mole ratio is from about 5.0 to about15.0; (2) a mixture comprising:(a) a complex of a nickel (O) compoundand a phosphine PR' where R' is as defined above; and (b) an alkylaluminum halide or aluminum trihalide; wherein components (2)(a) and(2)(b) are present in relative amounts such that the Al/Ni mole ratio isfrom about 5.0 to about 7.0; and (3) a mixture comprising:(a) a mixtureof a nickel (O) compound and a phosphine PR₃ ' where R' is as definedabove; and (b) an aluminum trihalide; wherein components (3)(a) and(3)(b) are present in relative amounts such that the Al/Ni mole ratio isfrom about 5.0 to about 7.0 and the P/Ni mole ratio is from about 1.0 toabout 2.0.
 2. The process of claim 1 wherein the dimerization catalystis a mixture comprising:(a) a nickel (II) compound selected frombis(2-ethylhexanoate) nickel; 2-ethylhexanoate nickel trihaloacetate;2-ethylhexanoate nickel o-chlorobenzoate; and 2-ethylhexanoate nickelacetylacetonate; (b) triarylphosphine; and (c) ethylaluminum dichloride.3. The process of claim 2 wherein the Al/Ni ratio is from about 9.0 toabout 15.0.
 4. The process of claim 2 wherein the triarylphosphine istriphenylphosphine, a tritolyl phosphine or atri(methoxyphenyl)phosphine.
 5. The process of claim 1 wherein thedimerization catalyst is a mixture comprising:(a) a complex of a nickel(O) compound and a phosphine PR'₃ where R' is as defined above; and (b)an alkyl aluminum halide or aluminum trihalide;wherein components (2)(a)and (2)(b) are present in relative amounts such that the Al/Ni moleratio is from about 5.0 to about 7.0; and the P/Ni mole ratio is fromabout 1.0 to about 2.0.
 6. The process of claim 1 wherein thedimerization catalyst is a mixture comprising:(a) a mixture of a nickel(O) compound and a phosphine PR₃ ' where R' is as defined above; and (b)an aluminum trihalide;wherein components (3)(a) and (3)(b) are presentin relative amounts such that the Al/Ni mole ratio is from about 5.0 toabout 7.0 and the P/Ni mole ratio is from about 1.0 to about 2.0 . 7.The process of claim 1 wherein the process is conducted at temperaturesin the range of from about -10° C. to about 100° C. and pressures in therange of from about 0 to about 2 atmospheres.
 8. The process of claim 1wherein the C₅ to C₁₄ olefin feed of the process comprises from about 70to about 100% by weight of linear C₅ to C₁₄ olefins.
 9. The process ofclaim 1 further comprising fractionally distilling the reaction productto recover a C₁₀ to C₂₈ olefin fraction containing linear andmono-branched C₁₀ to C₂₈ olefins.
 10. The process of claim 1 wherein thedimerization catalyst mixtures (1), (2) and (3) further comprise water.